EP2072543B1 - Gepfropfte Polymere - Google Patents

Gepfropfte Polymere Download PDF

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Publication number
EP2072543B1
EP2072543B1 EP07024684A EP07024684A EP2072543B1 EP 2072543 B1 EP2072543 B1 EP 2072543B1 EP 07024684 A EP07024684 A EP 07024684A EP 07024684 A EP07024684 A EP 07024684A EP 2072543 B1 EP2072543 B1 EP 2072543B1
Authority
EP
European Patent Office
Prior art keywords
meth
polymers
acrylates
integer
fatty alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP07024684A
Other languages
English (en)
French (fr)
Other versions
EP2072543A1 (de
Inventor
Florence Andrioletti
Stephanie Merlet
Jeremie- Lapere
Maria Da Silva Marques
William Lamarca
Benoit Abribat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cognis IP Management GmbH
Original Assignee
Cognis IP Management GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis IP Management GmbH filed Critical Cognis IP Management GmbH
Priority to EP07024684A priority Critical patent/EP2072543B1/de
Priority to AT07024684T priority patent/ATE512176T1/de
Priority to ES07024684T priority patent/ES2366965T3/es
Priority to PCT/EP2008/010492 priority patent/WO2009080213A1/en
Publication of EP2072543A1 publication Critical patent/EP2072543A1/de
Application granted granted Critical
Publication of EP2072543B1 publication Critical patent/EP2072543B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention is related to the area of polymers and refers to new comb polymers, a process for their production and their use as super-plasticizers or defoamers for concrete or plaster retarders.
  • Polyolefinic acids particularly polyacrylic acids, grafted with polyglycolethers and mono-methylpolyglycolethers (MPEG) and their use as additives for the manufacture of concrete are well known from literature. Examples for the state of the art can be found inter alia in FR 2776285 B1 (Chryso), EP 1260536 A1 (BASF) or WO 97/039037 A1 (Mbt).
  • WO 97/39037 A1 (Sandoz) describes the use of a styrene/maleic acid anhydride co-polymer, post esterified with a monomethoxy polyglycol ether for the same purpose; the maleate moiety, however, has a symmetric structure.
  • the products which can be found in the market either provide high fluidity to high-strength cement and concrete compositions or allow an extremely low water-to-cement or concrete ratio. Others reduce the decrease in fluidity, which takes place after a certain time, or control the generation of foam during the making of the final preparations. Unfortunately, none of these products provide a combination of all these properties on a satisfying level. Especially products allowing efficient foam control and to remove air bubbles in the early stage of the manufacture of the concrete show a strong tendency to separate from the mixture and form an organic layer.
  • the problem which underlies the present invention was to develop new polymers with improved super-plasticizing and retarding properties in order to overcome the disadvantages known from the state of the art.
  • the new polymers should allow simultaneously the establishment of an extremely low water-to-cement or concrete ratio, providing high slump retention while maintaining good flowability, and developing low foam during the preparation of the cement or concrete.
  • the present invention refers to grafted polymers, obtainable in that
  • the new polymers fulfil the complex requirements as outlined above. They provide high fluidity to high-strength cement and concrete while allowing low water-to-cement ratios. Good slump retentions is obtained, while flowability during this time is maintained. Especially, the products allow an effective control of foam generation and reduce the formation of air bubbles while the problem of surface layering is avoided.
  • Another object of the present invention concerns a process for the manufacture of grafted polymers comprising the steps of
  • Suitable monomethoxypolyethyleneglycol (meth)acrylates, forming component (b) usually follow general formula (I), CH 3 O(CH 2 CH 2 O) n OC-CR 1 CH 2 (I) in which R 1 stands for hydrogen or a methyl group and n denotes an integer of from 1 to 200, preferably 25 to 150 and more preferably 50 to 100.
  • Suitable products therefore show average molecular weights of 100 to 10000, preferably 200 to 6000 and most preferably 350 to 5000 Dalton.
  • Suitable C 12 -C 22 fatty alcohol+EO+PO (meth)acrylates, forming component (c), usually follow general formula (II), R 2 O(CH 2 CH 2 O) P1 (CHCH 3 CH 2 O) q (CH 2 CH 2 O) p2 OC-CR 1 CH 2 (II) in which R 1 stands for hydrogen or a methyl group, R 2 represents an alkyl or alkenyl radical having 12 to 22, preferably 16 to 18 carbon atoms, p1 and p2 independently stand for 0 or integers of 1 to 50, preferably 2 to 20, and q for an integer of from 1 to 50, preferably 2 to 20.
  • ethylene glycol (EO) and propylene glycol (PO) units in the monomer may be block wise or random. For example, it is possible to add a small quantity of EO to the fatty alcohol, followed by PO and optionally another quantity of EO in order to prepare a block polymer, or to mix the quantities of EO and PO, so that a randomised chain of alkylene oxide units is added to the alcohol.
  • fatty alcohol+EO+PO (meth)acrylates (component c) according to general formula (II) can be used, in which
  • component (b) is an adduct of 3 moles EO and 13 moles PO to cetyl stearyl alcohol, which is available in the market under the trademark Agnique ® DMF 250 (Cognis).
  • Polymerisation is conducted according to the state of the art. Components a, b and c are transferred into a flask where the polymerisation takes place.
  • the monomers can be used in a molar ratio (a):(b):(c) of from 1:(0.1-10):(0.1:10), preferably 1:(0.5:8):(0.5:8) and most preferably 1:(1-7):(1-7).
  • the polymerisation takes place in aqueous solution at elevated temperatures of 60 °C to 100 °C, and preferably 80 °C and is initiated by the addition of a conventional starter, such as, for example, ammonium persulfate.
  • the reaction mixture is cooled down and treated with an alkaline base, preferably an aqueous sodium or potassium hydroxide solution in a quantity sufficient to neutralise the acidic functions in the polymer and to prepare salts.
  • an alkaline base preferably an aqueous sodium or potassium hydroxide solution in a quantity sufficient to neutralise the acidic functions in the polymer and to prepare salts.
  • the products are diluted by addition of water in order to adjust the desired active matter content of typically 20 to 50 % b.w., and preferably 35 % b.w.
  • the grafted polymers obtained according to the present invention provide high fluidity and better workability to cement, concrete and plaster compositions.
  • Another object of the present invention is therefore the use of said new polymers as so-called super-plasticizers and/or defoamers for concrete or plaster retarders.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Claims (10)

  1. Pfropfpolymere, die dadurch erhältlich sind, daß man
    (a) (Meth)acrylsäure,
    (b) Monomethoxypolyethylenglykol(meth)acrylate und
    (c) C12-C22-Fettalkohol+EO+PO(meth)acrylate einer Copolymerisation unterwirft und das so erhaltene Reaktionsprodukt danach mit einer alkalischen Base neutralisiert und in Wasser solubilisiert.
  2. Verfahren zur Herstellung von Pfropfpolymeren, bei dem man:
    (i) Mischungen von
    (a) (Meth)acrylsäure,
    (b) Monomethoxypolyethylenglycol(meth)-acrylaten und
    (c) C12-C22-Fettalkohol+EO+PO(meth)acrylaten
    einer radikalischen Polymerisation unterwirft,
    (ii) die Säuregruppen der so erhaltenen Polymere mit Hilfe einer alkalischen Base neutralisiert und
    (iii) die neutralisierten Polymere in Wasser solubilisiert.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man Monomethoxypolyethylenglykol(meth)acrylate (Komponente b) gemäß der allgemeinen Formel (I) verwendet:

            CH3O(CH2CH2O)nOC-CR1=CH2      (I)

    worin R1 für Wasserstoff oder eine Methylgruppe steht und n eine ganze Zahl von 1 bis 200 bedeutet.
  4. Verfahren nach Anspruch 2 und/oder 3, dadurch gekennzeichnet, daß man Fettalkohol+EO+PO(meth)-acrylate (Komponente c) gemäß der allgemeinen Formel (II) verwendet:

            R2O(CH2CH2O)p1(CHCH3CH2O)q(CH2CH2O)p2OC-CR1=CH2      (II)

    worin R1 für Wasserstoff oder eine Methylgruppe steht, R2 für einen Alkyl- oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen steht, p1 und p2 unabhängig voneinander für 0 oder ganze Zahlen von 1 bis 50 stehen und q für eine ganze Zahl von 1 bis 50 steht.
  5. Verfahren nach einem der vorhergehenden Ansprüche 2 bis 4, dadurch gekennzeichnet, daß man Fettalkohol+EO+PO(meth)acrylat-Blockpolymere (Komponente c) gemäß der allgemeinen Formel (II) verwendet, worin R2 für eine Alkylgruppe mit 16 bis 18 Kohlenstoffatomen steht, p1 für eine ganze Zahl zwischen 1 und 5 steht, p2 für 0 steht und q eine ganze Zahl zwischen 10 und 15 bedeutet.
  6. Verfahren nach einem der vorhergehenden Ansprüche 2 bis 4, dadurch gekennzeichnet, daß man statistisch aufgebaute Fettalkohol+EO+PO(meth)-acrylat-Polymere (Komponente c) gemäß der allgemeinen Formel (II) verwendet, worin R2 für eine Alkylgruppe mit 16 bis 18 Kohlenstoffatomen steht, p1 und p2 für eine durchschnittliche ganze Zahl zwischen 1 und 5 stehen und q eine durchschnittliche ganze Zahl zwischen 10 und 15 bedeutet.
  7. Verfahren nach einem der vorhergehenden Ansprüche 2 bis 6, dadurch gekennzeichnet, daß man die Monomere (a), (b) und (c) in einem Molverhältnis von 1:(0,1-10):(0,1-10) verwendet.
  8. Verfahren nach einem der vorhergehenden Ansprüche 2 bis 7, dadurch gekennzeichnet, daß man die Polymere zum Erhalt einer wäßrigen Lösung, die einen Wirkstoffgehalt von 20 bis 50 Gew.-% zeigt, solubilisiert.
  9. Verwendung von Pfropfpolymeren nach Anspruch 1 als Verflüssigungsmittel für Beton- oder Putzverzögerer.
  10. Verwendung von Pfropfpolymeren nach Anspruch 1 als Entschäumer für Beton- oder Putzverzögerer.
EP07024684A 2007-12-20 2007-12-20 Gepfropfte Polymere Not-in-force EP2072543B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP07024684A EP2072543B1 (de) 2007-12-20 2007-12-20 Gepfropfte Polymere
AT07024684T ATE512176T1 (de) 2007-12-20 2007-12-20 Gepfropfte polymere
ES07024684T ES2366965T3 (es) 2007-12-20 2007-12-20 Polímeros injertados.
PCT/EP2008/010492 WO2009080213A1 (en) 2007-12-20 2008-12-11 Grafted polymers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07024684A EP2072543B1 (de) 2007-12-20 2007-12-20 Gepfropfte Polymere

Publications (2)

Publication Number Publication Date
EP2072543A1 EP2072543A1 (de) 2009-06-24
EP2072543B1 true EP2072543B1 (de) 2011-06-08

Family

ID=39386464

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07024684A Not-in-force EP2072543B1 (de) 2007-12-20 2007-12-20 Gepfropfte Polymere

Country Status (4)

Country Link
EP (1) EP2072543B1 (de)
AT (1) ATE512176T1 (de)
ES (1) ES2366965T3 (de)
WO (1) WO2009080213A1 (de)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4705525A (en) * 1985-06-28 1987-11-10 Ciba-Geigy Corporation Water-soluble or water-dispersible graft polymers, process for their preparation and the use thereof
DE4424818A1 (de) * 1994-07-14 1996-01-18 Basf Ag Niederviskose Mischungen aus amphiphilen nicht-ionischen Pfropfcopolymeren und viskositätserniedrigenden Zusätzen
US5614017A (en) * 1996-03-26 1997-03-25 Arco Chemical Technology, L.P. Cement additives
GB9607570D0 (en) 1996-04-12 1996-06-12 Sandoz Ltd Improvements in or relating to organic compounds
FR2776285B1 (fr) * 1998-03-19 2000-06-09 Chryso Dispersant hydrosoluble ou hydrodispersable pour compositions de ciment et suspensions aqueuses de particules minerales, et adjuvants contenant un tel dispersant
DE10125238A1 (de) 2001-05-22 2002-11-28 Basf Ag Wasserlösliche Polymerisate von Estern aus Acrylsäure, Methacrylsäure und Alkylpolyalkylenglykolen
EP1319676A1 (de) 2001-12-14 2003-06-18 Cognis Iberia, S.L. Anionpolymere
ATE423145T1 (de) 2002-09-07 2009-03-15 Cognis Ip Man Gmbh Anionpolymere
EP1657260A1 (de) 2004-11-12 2006-05-17 Cognis IP Management GmbH Anionpolymere

Also Published As

Publication number Publication date
ES2366965T3 (es) 2011-10-27
WO2009080213A1 (en) 2009-07-02
EP2072543A1 (de) 2009-06-24
ATE512176T1 (de) 2011-06-15

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